Freeze stabilized latex coatings



Patented July 13, 1954 FREEZE STABILIZED LATEX COATINGS Harvey T. Gehring, ChicagoJlL, assignor to The Sherwin a corporation of Ohio -Wiiliams Company, Cleveland, Ohio,

No Drawing. Application February 25, 1952, Serial No. 273,347

13 Claims.

. i This invention relates to water-containing coating compositions containing polymeric or- 1ganic material dispersed therein in finely divided orm.

More particularly the invention relates to a means of stabilizing emulsion polymers useful in coating compositions from breakdown due to alternate freezing and thawing of the aqueous or continuous phase.

Specifically, this invention relates to the use of ureides in conjunction with an emulsion polymer system of the .oil-in-water class. In the preferred form of the invention, use is made of monovinyl aromatic hydrocarbon units and aliphatic conjugated diolefin units polymerized together through the exercise of emulsion polymerization techniques. Addition of certain ureides to the resultant latex contributes to the capacity of the emulsion system to resist coagulation or emulsion breakdown due to extreme variations in temperature. 1

Experience indicates that breakdown due to freezing and thawing of emulsion systems is indirectly related to the disperse phase, but more directly with the nature and composition of the continuous aqueous phase. From this, it is obvious that the addition of ureides is undoubtedly also useful for the same purpose in latices formed by dispersion in water of bulk polymers after their formation. However, latex systems formed in this manner are presently of less interest for the production of commercial emulsion-type coating compositions than those formed by or through emulsion polymerization techniques.

In the past several years, the commercial importance of emulsion-type compositions for coating purposes has developed to the'extent of being a major replacement for the conventional solvent-type coatings useful for finishing and redecorating interior wall areas. Freedom from solvent odor, ease of application, freedom from fire hazard and economy in use have, contributed materially to consumer acceptance of emulsiontype protective and decorative coatings.

Advent of large consumer demand has meant increased inventories of finished latex emulsion paints, and in turn, has brought into focus the problem of storage and handling of water-containing materials under a variety of weather conditions. Without doubt, the greatest hazard in handling and storage of emulsion paints containing water in the continuous phase, arises from storage and handling at freezing temperatures. Often in either shipment or storage, large quantities of these materials freeze. Upon subsequent thawing, the coating composition loses fluidity and can no longer be satisfactorily applied by brushing. The lot frozen becomes a total loss. While heated warehousing and heated shipping means offer a solution, this solution is impractical over a nation-wide distribution system.

It is the object of this invention to provide a method of stabilizing a paint latex emulsion polymer system against breakdown and deterioration due to alternate freezing and thawing by addition thereto of a quantity of a watersoluble ureide.

It is more specifically an object of this invention to provide a more universally useful paint latex which comprises an oil-in-water emulsion polymerization product of an aromatic vinyl compound containing a single center of unsaturation and. a, conjugated diolefin as the primary components containing a stabilizing amount of a water-soluble ureide.

It is the specific object of this invention to provide a pigmented, oil-in-water emulsion-type coating composition capable of depositing a continuous film when dry, containing a disperse phase comprising an emulsion polymer having at least mol percent of a monovinyl aromatic hydrocarbon of the benzene series havin a single center of unsaturation-and between 33 and 60 mol percent of an aliphatic conjugated diolefin in chemical combination, a continuous aqueous phase containing a protective colloid and a quantity of from about 1% to 15% based on said latex solids of a water-soluble ureide containing not more than four carbon atoms, if alkyl-substituted.

Stabilizers useful for the purposes of this invention include in the preferred form of the invention, urea and thiourea. Investigation of a homologous series of compounds similar in structure and related to urea have shown that monomethyl urea; dimethyl urea, both symmetrical and unsymmetrical; dimethylol urea; monoethyl urea; diethyl urea, both symmetrical and unsymmetrical; trimethyl urea; n-propyl urea; isopropyl urea and n-butyl urea, all of which are water-soluble, are useful for the purposes of this invention. Only thiourea of the analogous sulfur series of compounds was found to be of value, however. Water-insoluble homologs and analogs of urea, including, for example, isobutyl urea, pentyl urea and tetraethyl urea are water-insoluble and, hence, of no practical value for the purposes of prevention of emulsion breakdown. Tetraethyl urea, biuret, thiosemicarbazide, symmetrical diethyl urea, dfliut'yl thiourea and dibutyl urea were also tested and found to be of little interest. From the extensive laboratory investigation made to determine the scope of compounds useful for the-purposes of the invention, it has been found that water-soluble compounds containing the bivalent ureylene nucleus (J. A. C. S. 55, 3918, 1933) wherein R1 and R: are radicals selected from the group consisting of hydrogen, hydroxyl, alkyol and alkyl radicals containing not more than 4 carbon atoms wherein the sum of the carbon atoms in R1 plus R2 does not exceed 5, defines the scope of useful additives.

When the substituents on the ureylene nucleus are such that the resulting ureide compound is water-insoluble, the compounds are not practically useful for the purposes of the invention. The exploratory work among related compounds of urea for comparison of effectiveness were made upon an equal weight basis. Their use on an equal molar basis was checked, but very little diflerence was observed upon use of larger amounts. Large amounts of stabilizer are considered to be undesirable for the reason that water-soluble constituents in a paint film reduce washability of films deposited therefrom. Additionally, large amounts of the urea class of stabilizers have been found to affect the viscosity of the final product unduly. Excesses are also economically wasteful and should, if for no other reason than costs, be avoided.

The art of emulsion polymerization has reached practical utilization only recently and the patent art on the subject has been enriched tremendously since the rubber shortages of World War II. While pooling of general information by those working in the field has been generally practiced, much of the specific information on actual emulsion polymerization techniques known to specific groups in the art is still not generally available. Further, the great interest and emphasis in that art has been in the production of elastomers in bulk form for use as a replacement for rubber, e. g., in the massive form, and not for purposes of protective and decorative coatings. Presently, therefore, definitions of all the qualities and characteristics of emulsion polymers useful for coating purposes cannot be set forth as the art is very new. For this reason, the term paint latex" is used herein to refer to emulsion polymer systems. This for the reason that language in this art as it relates to the subject at hand is, like the art, quite undeveloped. These latices are also referred to by some who are employed in the art as reverse rubbers" for the reason that the proportions of aromatic vinyl compound and diolefin are in reverse ratio to the usual copolymer rubbers used in massive form for the manufacturing of tires, etc.

The term paint latex" or "reverse rubber latices," as adapted herein, refers to the concept of a dispersed phase polymer formed or polymerized in an aqueous carrier, the oil-in-water type emulsion resulting having specific physical haracteristics and preferably certain chemical constituents, as herein set forth.

More specifically, the term paint latex or reverse rubber latex includes particularly, but is not known to be limited to, the products of emulsion polymerization. The emulsion polymers produced from two or more unsaturated poly-. merizable components in the presence of surface active agents of non-ionic and anionic character as stabilizers and one or more per-compounds, e. g., peroxides, persulfates, etc. as accelerators of polymerization in such manner and proportions as to form an aqueous emulsion polymer system produce the preferred latices. All of the paint latices of interest to this invention which have been examined in detail have a particle diameter of the disperse phase in excess of 0.2 micron and preferably from 0.2 to about 0.4 micron. The pH of the aqueous phase is from 7.5 to 11 and preferably from 8.0 to 10, and the water content is not more than 60%, usually from to of the total weight of the emulsion polymer. A further essential characteristic of materials included in the term paint latex" is that the latex or blend of two or more latices to qualify for paint and related coating usage and to bear the name paint latex" shall be capable of agitation in a malted milk-type 1 drink mixer at a rate of rotation of the agitator of 12,000 R. P. M. for one-half, hour without show ing graining, viscosity change or other characteristic evidences of emulsion breakdown. Latices not meeting the above specifications are not useful for coatings and are excluded from the scope of the term paint latex" as used herein.

Presently, the most useful paint latices are copolymers and terpolymers comprising monovinyl aromatic hydrocarbons and aliphatic conjugated diolefines containing not more than 67 mol percent of the monovinyl aromatic hydrocarbon and not more than mol percent of the aliphatic conjugated dioleflne.

. and 2,479,967. The term paint latex includes I hydrocarbon.

the product of a single emulsion polymerization, or a blend of two or more emulsion polymerization products. However, to qualify as a paint latex, the single product or the blend of oil-inwater emulsion products utilized as the paint latex must be capable of depositing a continuous film from the disperse polymer containing phase. Having thus described the scope of the term "paint latex" as accurately as the present state of knowledge concerning-this class of composition will allow, the term shall be understood to include all of the limitations as set forth above. As is presently known, most of the paint latices available from commercial latex producers using emulsion polymerization techniques employ principally butadiene 1,3 as the aliphatic conjugated dioleflne and styrene as the aromatic vinyl compound containing a single reactive center of unsaturation as the essential monovinyl aromatic Isoprene and vinyl toluene are illustrative of the other useful combinations.

In researches toward practical paint formulations of emulsion-type coating compositions, I have found that emulsion copolymers of the butadiene-styrene class containing about by weight of styrene will not deposit continuous films, but may be blended with additional quantities of emulsion polymers of the same class containing as little as 40 mol percent styrene to Drink Master Model #30-Hamilton Beach Company.

Latices within this class are described in U. 8. Patents 2,498,712

the first description will generally withstand.

freezing and thawing without breakdown, but when combined with emulsions having a plasticizing effect to form continuous films; as with emulsion polymers of the second description, are prone to break and become useless in protective and decorative emulsion coatings. From many laboratory tests, it appears to be a general rule that when a latex is compounded suitable to deposit continuous films as is essential to a. completed paint latex formulation for coating purposes, they acquire the faulty characteristic of lack of stability upon alternate freezing and thawing.

It is obvious that emulsion paints, both of the pigmented and clear class, intended for storage and shipment the year around in temperate climates are subject to freezing. Upon freezing, all of the paint latices of commerce (except for odd and inconsistent batches) tested to date break down and become valueless after several freezing and thawing cycles. Accordingly, research has been extensive to find ways of making latex coatings for paint and allied purposes stable against this natural phenomenon, for great financial losses may be suffered when shipments of material are made during severely cold weather. From general experience in this field, it has been observed that latices vary in their emulsion stability (particularly in relation to freezing) depending upon the kind and amount of ionic and non-ionic emulsifier and other materials used in their manufacture in small amount and other characteristics of the latex as are inherent in the techniques known only to the original producer. It has been observed, however, that the freeze and thaw cycle stability of the various latices commercially available is enhanced by the addition of from about 1% to of a stabilizer of the class herein described based upon the paint latex solids in the coating composition, but the preferred range has been found to lie in the range of from about 4% to 8% by weight based on said solids content. Thus, if a paint latex will withstand one freezing and thawing cycle, the addition of a ureide as described herein permits further cycling without deterioration, impossible without the additive.

As previously indicated, the useful freeze stabilizing additives for my purpose include compounds containing a ureylene nucleus broadly and urea and thiourea specifically. Urea is by far the most promising stabilizer as it is available commercially of good purity, is economical in cost and is more effective on a purely weight basis than any of the other materials closely related thereto which may be used as substituents therefor. While thiourea is useful and is claimed in my copending application filed of even date herewith, U. S. Serial 273,348, substituted thioureas are of practically negligible value. The stabilizers of particular value are defined broadly as water-soluble compounds having a ureylene nucleus which, if substituted, contain not more than 5 carbon atoms and not more than 4 carbon atoms in any one substituent aliphatic group. Further not less than 1 hydrogen atom can be directly associated with each of the nitrogen atoms of the parent ureide. Water solubility appears to be essential.

The principle behind the use of ureides as freeze stabilizers is not understood, but it is clear from experimental results that the action is not that of the effect of ionizable salts upon the 6 freezing point of water. Ionic inorganic salts have an adverse effect in emulsion type paint coatings upon emulsion stability and should be avoided generally.

The following examples are illustrative but not to be taken as limiting upon the scope of the improvement herein described.

EXAMPLE 1 An emulsion copolymer of commerce 1 contain-- ing 45% solids of which 40 parts were butadiene by weight and 60 parts by weight were styrene were frozen and allowed to thaw. Upon thawing, the viscosity had increased and the material coagulated to a. point no longer useful.

EXAMPLE 2 Two hundred parts of the above emulsion copolymer were combined with 6.3 parts of urea. The sample was alternately taken down to 10 degrees below zero F. and up to '77 degrees F. for 4 successive times. The sample showed no apparent changes in viscosity or emulsion stability and could be used to deposit a clear coating of continuous nature.

EXAMIPLE3 EXAMPLE 4 A 200 gram sample of the above latex (Example 3) was combined with 13 parts of urea and subjected to freezing and thawing as in Example 3. After 4 cycles, the latex was not visibly affected and was used to deposit a clear coating on paper.

EXAMPLE 5 A third emulsion copolymer of commerce 3 containing 33 percent of butadiene and 67 percent of styrene by weight and meeting all of the tests of a paint latex as hereinbefore set out was subjected to a freeze and thaw cycle. After reaching room temperature, the physical nature of the emulsion was such as to be unsuited for further use in paint formulations of the emulsion ty EXAMPLE 6 200 parts by weight of the emulsion copolymer of Example 5 were combined with 9 parts by weight of urea. After solution of urea in the aqueous continuous phase, the material was subjected to freezing and thawing without materially affecting the physical character of the emulsion system.

EXAMPLE 7 parts of an emulsion polymer of commerce 4 containing 80 percent styrene and 20 percent of butadiene by weight (found not to lay down a continuous film by itself) was combined with parts of an emulsion polymer of commerce as described in Example 1 (which does deposit a. continuous film). parts of the mixture were frozen and thawed. Upon thawing out to room temperature, the mixed polymeric disper- 1 Dow Chemical Compan 512-K.

3 Firestone Tire and Bu ber Company F-4 Latex. I Dow 762-K.

Dow Chemical Company 529-K.

7 slons in water were found to be unsuited for costing purposes.

EXAMPLE 8 To the second aliquot portion of 100 parts of the mixture of Example 7 were added 2 parts of urea. After the urea had been dissolved in the aqueous phase, the emulsion system was subjected to degrees below zero F. temperatures overnight and thawed to 77 degrees F. the following day. The viscosity of the product had not been changed appreciably by the; treatment and the coating laid down a continuous film on paper.

EXAMPLE 9 Same as Example 2, with the substitution of thiourea for urea. Comparable results were obtained.

EXAMPLE 10 Same as Example 4, but thiourea was substituted for urea. Similar stability was observed as with urea.

EXAMPLE 11 Same as Example 6, but thiourea was substituted for urea. There was some indication that on equal weight substitution, thiourea was not quite as effective as urea. However, the resultant material after thawing deposited a continuous film upon paper.

EXAMPLE 12 A series of tests as in the above Examples 1-8 was made substituting butyl urea for urea. Butyl urea was found slightly less effective than urea and thiourea when used on an equal weight substitution basis, but was effective.

EXAMPLE 13 A series of tests were run as described in Examples 18 above, substituting symmetrical dimethyl urea for urea. While slightly less effective as a stabilizer than urea, the results were useful for the purpose and prevented emulsion breakdown of the latex due to freezing.

EXAMPLE 14 A series of tests as described in Examples 1-8 were carried out substituting dimethylol urea for urea on an equal weight basis. The dimethylol carbamide was found to have a stabilizing effect upon the latices tested against breakdown by alternate freezing and thawing.

EXAMPLE 15 Biuret was tested in lieu of urea as the stabilizer additive as in Examples 1-8. Practically no stabilizing effect was observed.

EXAMPLE l6 Symmetrical diethyl thiourea was tested in lieu of urea as the stabilizer additive as in Examples l-8. Freeze stability was not noticeably improved thereby.

EXAMPLE 17 Hydroxy urea was tested in a series of examples similar to 1-8, substituting it for urea. A similar improvement in freeze stability of the latices was observed as with urea.

EXAMPLE 18 Two quarts of two different commercial emul 8 and not suitable as paints'as to application characteristics. The samples containing the additive were still useful after the cycle test.

The following examples are further illustrative of latex emulsion paint formulations which have been improved in each instance in their ability to withstand ultimate freezing and thawing cycles by the addition of u-"-" .ereto.

Stabilizer solution 75 parts dried acid precipitated casein and 412 parts of water were weighed into a jacketed vessel equipped with an agitator. The temperature of the slurry was increased to 160 degrees F. after which 10 parts of sulfonated tallow and 8 parts of sodium pentachlorophenate, 5 parts of borax and 5 parts of 26 degree Baum ammonia were added and stirred into the aqueous solution. Thereafter the temperature was increased to 170 degrees F. and held for a half hour. This solution was then drawn ed for use in the preparation of some of the following examples.

Stabilizer solution 8" 380 parts of water and 60 parts of dried soya protein were weighted into a jacketed mixing EXAMPLE 19 Oil-modified Later: paint Parts Lithopone Rutile T10: Ferrite yellow 2 Black iron oxide 2 Mica 40 Clay 65 Lorite (75% calcium carbonate and 25% diatomaceous silica) 60 Sodium salt of alkyl aryl sulfonate 3 Tetrasodium pyrophosphate 2 Soya protein solution (stabilizer solution B) 1'75 Water 188 were thoroughly mixed together. Thereafter 45 parts of four-minute heat bodied linseed oil, 1 part of 25% lead naphthenate, 3 parts of 6% cobalt naphthenate and 4 parts of pine oil were added to the pigment slurry. After incorporation of the oils and driers, the pigment slurry was passed through a zone of high shear (e. g., a colloid mill) into a thin-down vessel. Thereafter 300 parts of a paint latex and 6 parts of urea were mixed into the milled emulsion. The paint latex contained 200 parts of a 45% solids emulsion copolymer containing approximately 60% styrene and 40% butadiene and 100 parts of an emulsion copolymer containing 80% styrene and 20% butadiene.

EXAMPLEZO Drackett 220 orthoprotein.

' National Lead Company.

" Dow Chemical Company 5121!. 3 Dow Chemical Company 529K.

LE 21 EXAMPLE 26 so protein Maud mm m Sodium carbon! methyl cellulose stabilized latex paint Uthopone 50 n 300 Rutfle T10: 240, 3, 55

60 Rutile Ti mm Ultramarine blue 50 Pigment een R were thoroughly incorporated into 165 parts of m Mica gr 1 40 stabilizer solution "B" along with 140 parts of Tetmsodmm pyrophosphate 2 water containing 2 parts of tetrasodium pyrosodium cal-boxy methyl (high viscosity) 5 phosphate and 2.5 parts of sodium alkyl aryl Alkylolamide lsifying agent; 15 sulionate. To the aqueous slurry of pigment sodium polyacrylate 1a 10 were added 10 parts of sulionated tallow and 30 I5 Suuomwd tanow (anmoam) 10 parts of a four-minute heat bodied linseed oil Foubminute'heat bodied linseed n 45 containing 1 part of 25% lead naphthenate and 25% lead naphthenate 1 2 parts of 6% cobalt naphthenate. after thor- 3% cobalt mphthenate 3 ough incorporation of the above ingredients, the water 0 mass was passed through a zone of high shear Pine 01] 4 to produce a uniform emulsion and dispersion and collected in a thin-down vessel equipp d with an The above ingredients were th y mixed agitator. Thereafter 425 parts of a 45% solids together and passed throu h a lloid mill into paint latex, 200 parts of water and 15 parts of reducing vessel. To the milled material was addurea were added to the milled mass. The yield ed 343 Darts 01 8 Solids p t at d 12 was 125 gallons of latex emulsion paint. P ts of u a. h yi ld was 100 all ns f r adyto-apply emulsion paint. W 22 The above examples are believed to illustrate fully the best mode of practicing my invention. The above example was repeated with the sub- 3 be t illuminating to point out that summon of a paint latex containing ammxlmatfi e commercial latices available "ary from batch 1y 62% styrene and 38% butadienep batch, and give inconsistent results which are disconcerting, particularly as to freeze stability. EXAMPIE 23 For example, certain latices have not been freeze stable by themselves, but exhibit improved freeze Same as Example 21 except a paint latex conresistance after pigmentation. However, upon taining 60% styrene and butadiene was addition oi the described ureides as stabilizers, substituted. said latices pass freeze tests both pigmented and non-pigmented. Another lot of the same latex EXAMPLE 24 40 will lack stability even after pigmentation, but upon addition of a ureide oi. the class described, Oil free casein stabilized latex paint Wm pass freeze stability tests In an instances Parts stability against freezing and thawing cycles was Rume 20o improved by the method disclosed. Lithopone 100 In general. the higher the degree of substitutior Mica 25 of the ureylene nucleus, the less efl'ective are ad- Clay 75 ditives in their stabilizing eflfects.

Having thus described the best mode or accom- Ei2 fl$m%i1f?f?? f::31:13:31: 193 pushing the ends or my meme 1 Pine 4 5o 1. A method of stabilizing an emulsion cowater 112 polymer comprising an aromatic vinyl compound containing a single center of unsaturation and m m ed an passed over a colloid a comugated dioiefln having the qualities essenill t o l fe u llifoi m disp ersion oi the pigmento Paint latex which comprises dispersing tary mabeflaL To the milled pigment slurry was therein irom 1% to 15% or a water-soluble comadded 425 parts oi a 45% solids paint latex con- Pmmd inin a ureylene nucleus taining 87% styrene and 33% butadiene copoly- H merized by emulsion techniques." To the completed paint was added 12 parts of urea as a freeze stabilizing additive. The yield was approximately 100 gallons. H

Ra Example 25 was similar to Example 24 with the substitution or a paint latex containing 60% wherein R1 and Re are radicals selected from the styrene and 40% butadiene as the components group consisting f y n. hydroxyl. alky Of an emulsion copolymen This latex contained and alkyl radicals containing not more than four approximately 45% solids}; carbon atoms wherein the sum 0! the carbon atoms in R1 plus Ra does not exceed 5.

g lggcon i Nl z s li'. Co E m C me 762K 2. As in claim 1, wherein the water-soluble mu ll 0 l. eol l ti i nlh is atyren ll 83% butadie g approx. compound 15 urea B one Dow Chemical Company 512K. 1: ginol Laboratory 2012A.

odical VD. i: zl'eg i lfga z be l- 2% ii x ioov. 62% styrene-38% butadiene latex (Firestone F-d).

3. As in claim 1, wherein the water-soluble compound is hydroxy urea.

4. As in claim 1, wherein the water-soluble compound is diethyl urea.

5. As in claim 1, wherein the water-soluble compound is dimethylol urea.

6. As in claim 1, wherein the water-soluble compound is n-butyl urea.

7. A pigmented oil-in-water emulsion type coating composition capable of depositing a continuous film when dried including as the princi, binder therein an emulsion copolymer or a major proportion of an aromatic monovinyl compound havinga single center or unsaturation and a minor proportion of butadienehaving' a particle size at least 0.2 microns in diameter and characterized by its ability to withstand subjection to high shear ratesdfor extended periods of time without graining and from 4% to 8% by weight of said copolymer solids of a watersoluble compound containing a ureylene nucleus wherein R1 and R2 are radicals selected-from the groupconsisting of hydrogen, hydroxyl, alkyol and alkyl radicals containing not more than four carbon atoms wherein the sum of the carbon atoms in R1 plus B: does not exceed 5.

8. As in claim "I, wherein the water-soluble compound is urea. V

9. As in claim '1, wherein the water-soluble compound is hydroxy urea.

10-. As in claim '7, wherein the water-soluble compound is diethyl urea.

11. As in claim '7, wherein the water-soluble compound is dimethylol urea.

12. As in claim 7, wherein the water-soluble compound is n-butyl urea.

13. In a pigmented oil-in-water emulsion type coating composition capable of depositing a continuous film when dry containing a disperse phase consisting essentially of an emulsion polymer having at least mol percent or a monovinyl aromatic hydrocarbon of the benzene series having a single center of unsaturation and between 33 and mol percent of an aliphatic conjugated dlolefin in chemical combination and a continuous aqueous phase containing a protective cclolid, the improvement which comprises including in said aqueous phase of stabilizing quantities of a water-soluble compound containing a. ureylene nucleus whose substitutent groups in total contain not more than four carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,392,135 Farr Jr. Jan. 1, 1946 2,427,326 Goodloe et a1. Sept. 9. 1947 2,519,348 Burnell et a1. Aug. 22, 1950 2,595,956 Kunze et a1. May 6, 1952 

1. A METHOD OF STABILIZING AN EMULSION COPOLYMER COMPRISING AN AROMATIC VINYL COMPOUND CONTAINING A SINGLE CENTER OF UNSATURATION AND A CONJUGATED DIOLEFIN HAVING THE QUALITIES ESSENTIAL TO A PAINT LATEX WHICH COMPRISES DISPERSING THEREIN FROM 1% TO 15% OF A WATER-SOLUBLE COMPOUND CONTAINIGN A UREYLENE NUCLEUS 